|Publication number||US3639304 A|
|Publication date||Feb 1, 1972|
|Filing date||Jun 27, 1968|
|Priority date||Jun 27, 1968|
|Publication number||US 3639304 A, US 3639304A, US-A-3639304, US3639304 A, US3639304A|
|Inventors||Charles F Raley Jr|
|Original Assignee||Dow Chemical Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (34), Classifications (22)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Feb. 1, 1972 c. F. RALEY, JR 3,639,304
INVENTOR. Char/es fl Ao/ey Jn United States Patent ABSTRACT OF THE DISCLOSURE A flame retardant or selfextinguishing foamed polyethylene useful as insulation is described. This new composition contains a ternary mixture of flame-retardant agents containing certain amounts of (1) an antimony compound, (2) a halogen-containing aliphatic or cycloaliphatic compound having certain specificities, and (3) a bromine-containing aromatic or acyclic compound of a particular class.
The present application is a continuation-in-part of copending application Ser. No. 606,577, filed I an. 3, 1967, now abandoned.
This invention relates to flame-retardant or self-extinguishing polyethylene foam.
It has been proposed heretofore to impart flame retardancy to polyethylene by incorporating various materials in the polyethylene. Flame retardance has been obtained, for instance, by combining with the polyethylene a solid chlorinated hydrocarbon of high chlorine content such as chlorinated paraffin, and an inorganic flame-retardant substance such as antimony oxide in critical proportions to each other and to the polyethylene. Such compositions are described in U.S. Pats. 2,480,298, 2,590,211, and 2,669,521.
These prior art compositions are generally directed to the making of flame-retardant solid polyethylene, but are not satisfactory for the purpose of making self-extinguishing polyethylene foam.
Accordingly, it is a primary object of this invention to provide flame-retardant or self-extinguishing foamed polyethylene compositions which are not heavily loaded with flame-retardant agents yet produce foamed products possessing highly satisfactory self-extinguishing times of 3 or 4 seconds or less. Another object is to provide flame retardant or self-extinguishing foamed polyethylene compositions which contain a smaller and more desirable concentration of flame-retardant agents than has hereinbefore been used.
I have now discovered that when 12 to 16 parts by weight of a ternary mixture of flame-retardant agents containing certain amounts of (1) an antimony compound, (2) a halogen-containing aliphatic or cycloaliphatic compound having a hydrogen atom or halogen atom attached to a carbon atom alpha to a halogen-substituted carbon atom and containing from about 50 to 80 percent by weight of halogen as the active self-extinguishing agent, and (3) a bromine-containing aromatic or acyclic compound, the acyclic compound either containing vinylic bromine or not having a hydrogen atom or bromine atom attached to a carbon atom alpha to a bromine-substituted carbon .atom, as the passive self-extinguishing agent, is intimately incorporated in 100 parts by weight of polyethylene foam, unexpectedly good selfextinguishing properties are obtained. In contrast, when the same total "ice amount of a mixture of flame-retardant agents which contain only agents (1) and (2) is incorporated in 100 parts of polyethylene foam, a foamed material having vastly inferior self-extinguishing properties is obtained.
In accordance with the present invention, the ternary flame-retardant system incorporated in the polyethylene foam contains the flame-retardant or self-extinguishing agent in the weight ratios within the area ABCDEF of the accompanying drawing.
The accompanying drawing is a trilinear diagram wherein the antimony compound is (1), the halogen-containing aliphatic or cycloaliphatic compound having a hydrogen atom or halogen atom attached to a carbon atom alpha to a halogen-substituted carbon atom and containing from about 50 to about percent by weight of halogen is (2), and the bromine-containing aromatic or acylic compound, said acyclic compound containing vinylic bromine or not having a hydrogen atom or bromine atom attached to a carbon atom alpha to a bromine-substituted carbon atom is (3). Maximum and minimum weight ratios of components are shown in the drawing by equations such as (1)/(2) =05.
The extreme weight limits of each component, per parts of polyethylene, are from 3.3 to 10.0 parts by weight of (1) above, 3.0 to 10.6 parts by weight of (2) above, and 0.4 to 3.9 parts by weight of (3) above, but these limits are subject to the above described ratios.
Surprising as it may seem, use of the three different types of flame-retardant agents in admixtures in the proportions herein prescribed provides uniquely superior and entirely unpredictable results. Thus, by preparing the foamed polyethylene compositions of the inventions, products of unexpectedly and significantly superior selfextinguishing properties are obtained.
The antimony compounds useful in the practice of the invention include antimony trioxide, antimony pentoxide, antimony sulfide and the like.
The halogen-containing aliphatic or cycloaliphatic compounds having a hydrogen atom or halogen atom attached to a carbon atom alpha to a halogen-substituted carbon atom which can be used in the practice of the invention include the chlorinecontaining compounds such as hexachlorocyclohexane, a chlorinated paraffin wax containing between 50 and 80 by weight of chlorine, and the like, as well as the bromine-containing compounds such as pentabromomonochlorocyclohexane, hexabromocyclohexane, tris (2,3-dibromopropyl)phosphate, brominated polybutadiene latex, and the like. Preferably, these compounds contain from 3 to 40 carbon atoms. These materials function as active or thermally unstable self-extinguishing agents which act to confer good resistance to burning for the first several ignitions but then fall off in effectiveness.
The bromine-containing compounds which can be used in the practice of the invention include aromatic compounds such as hexabromobenzene, pentabromomonochlorobenzene, tetrabromodichlorobenzene, tetrabromobenzene, pentabromophenol, tetrabromobisphenol-A, bis (pentabromophenyl) ether, and tri-bromophenol, as well as acyclic compounds having vinylic bromine or not having a hydrogen atom or bromine atom attached to a carbon atom alpha to a bromine-substituted carbon atom, such as pentaerythrityl tetrabrornide, 2,2-bis(bromomethyl)-1-bromo-3-hydroxypropane, and the like. Preferably, the aromatic compounds contain from 6 to 12 carbon atoms in the aromatic ring structure, and the acyclic compounds contain from 3 to 15 carbon atoms. These agents function in the ternary self-extinguishing system as passive or thermally stable self-extinguishing agents which give poor performance for the first several ignitions but then act to give increasingly better results.
In the practice of the present invention, a homogenous mobile or flowable gel composition of heat-plastified or molten normally solid polyethylene, 12 to 16 parts per 100 parts of polyethylene of the ternary flame-retardant mixture hereinbefore described, and a volatile organic foaming agent is formed under pressure and thereafter said composition is extruded into a zone of lower pressure sufficient to cause expansion of the extruded material with resultant formation of a foamed flame-retardant polyethylene article composed for the most part of uniformly fine individually-closed thin-walled cells.
Small amounts, e.g. from 0.1 to 2 percent by weight of the polyethylene, of additives such as aluminum stearate, zinc stearate, indigotin, blue copper phthalocyanine or other agents such as finely divided calcium silicate, diatomaceous earth, calcium carbonate, barium sulfate and the like can be employed advantageously as nucleating agents, but are not required in the invention.
The mobile or flowable gel is prepared by placing the ingredients under pressure of the foaming agent, suitably at temperatures above the crystalline melting point of the polyethylene, e.g. at from 90 to 200 C., such as by heating the ingredients in admixture with one another in a pressure resistant vessel or an extruder until a homogenous or substantially uniform flowable gel is obtained. Thereafter, the gel is extruded into a zone of sufficiently lower pressure such as the atmosphere to cause the extruded material to expand with resultant formation of a cellular or foam body.
The gel is preferably extruded at a temperature near or above the melting point of the polyethylene, but higher or lower temperatures can be used. The temperature at which the gel is extruded into the zone of lower pressure will vary depending in part upon the size and arrangement of the apparatus used, the rate of extrusion of the gel, the melting point of the polyethylene and the proportion and kind of volatile organic foaming agent or other additives employed.
In general, the gel can be extruded at a temperature of from about C. below the temperature at which crystallization of the polyethylene causes an observable cloudiness of the gel, up to a temperature of 25 C. above the melting point of the polyethylene. The temperature at which crystallization of the polyethylene causes a cloudiness of the gel can be determined readily by a simple test such as by sealing weighed amounts of the polyethylene and the foaming agent in a glass tube, heating the mixture to a temperature above the melting point of the polyethylene to obtain a transparent uniform gel, then cooling or allowing the gel to cool and observing the temperature at which the gel becomes hazy or cloudy. The temperature at which an observable cloudiness of the gel occurs is hereinafter referred to as the cloud point.
The pressure to be maintained on the gel prior to extrusion into a zone of lower pressure should be at least about as high as that of the vapor pressure of the volatile organic foaming agent and sufiicient to prevent foaming in the extruder or discharge orifice. Pressures of from about 300 to 2,000 lbs./sq. in. or higher, gauge pressure, can be used.
The volatile organic foaming agent should be a nonsolvent or poor solvent for the polyethylene such as 1,2- dichlorotetrafiuorethane, dichlorodifluoromethane, iso butane, methyl chloride, 1,1,1-trifiuoroethane, ethylidene fluoride, perfluoropropane, 2,2 difiuoropropane, each alone or mixtures thereof and the like, but one that dissolves in the polymer in an amount of up to about percent by weight sufiicient to form a mobile or flowable gel and expand the extruded gel to produce a cellular or foamed body. The foaming agent can be employed in amounts of from about 0.05 to 0.5 gram mole per 100 grams of the polyethylene.
In practice, the flame-retardant polyethylene foams can be prepared by feeding solid granules of the polyethylene,
together with the ternary flame-retardant mixture in the desired proportion, into the feed hopper of a plastic extruder wherein the polymeric material is pressed and heated to its melting temperature and is forwarded by means of the screw into a mixing and blending zone wherein the heat-softened material is blended under pressure with a volatile organic foaming agent such as 1,2- dichlorotetrafluoroethane also fed to the mixing and blending zone of the extruder, to form a' homogenousmobile gel and is brought to a temperature between about and 200 C., preferably from 90 to 120 C., then is extruded into a zone of lower pressure, suitably the atmosphere, wherein the extruded material expands with resultant formation of a foam of substantially uniform fine individually-closed thin-walled cells.
An alternative method of foaming the composition is to incorporate a decomposable blowing agent such as azodicarbonamide, benzene sulfonyl hydrazide, oxybis benzene sulfonyl hydrazide, ammonium carbonate, N,N-dinitroso N,N-dimethyl terephthalamide, and the like, in the polymer composition along with the flame-retardant additives, heating the mixture above the softening point of the polymer to the decomposition point of the blowing agent, and permitting the liberated gas to expand the polymer composition into a foamed state.
The flame-retardant foamed polyethylene of the invention is useful as insulation, in packaging applications, for forming gaskets, as sealant backers in certain types of construction, etc.
The following non-limiting examples serve to illustrate my invention.
EXAMPLE I parts by weight of polyethylene having a melt index of 2, together with 8 parts of antimony trioxide, 6% parts of chlorinated paraffin wax containing about 70 percent chlorine and 1% parts of hexabromobenzene was compounded thoroughly in a Banbury mixer at temperatures between -150 C., such that the entiremass was plastified and homogenous, then cooled and ground up into fine particles. The compound mixture was fed into a plastics extruder at a rate corresponding to 5 pounds of the mixture per hour. The plastic extruder employed in the experiment comprised a barrel having a 1% in. diameter screw equipped with a mixing head similar in design to that described in US. Pat. 2,453,088. A sealing plate was positioned midway of the screw. An inlet to the barrel of the extruder was provided adjacent to the sealing plate for feed of a volatile organic compound as blowing agent into the barrel and into contact with a heat-plastified polyethylene. The sealing plate formed a constricted passageway between the rim of the plate and the bore of the barrel so that flow of the heat-plastified polyethylene through the constricted passageway by pressure of the flights of the screw formed an effective plastic seal against counter-current flow or leakage of the volatile organic compound from the extruder. The heat-plastified polyethylene formation was forwarded under pressure of the screw around the sealing plate and into the second section of the barrel of the extruder wherein it was mixed with 1,2-dichlorotetrafluoroethane as a foaming agent fed thereto at a rate of 0.8 lb./ hr. The resulting mixture was blended under pressure e.g. 500-600 lbs/sq. in..gauge, principally by action of the mixing head on the screw of the extruder, into a uniform gel composition and was brought to a temperature of 112 C., then was forced through a discharge orifice of A x /8 in. cross-section into the atmosphere. The. extruded material was allowed to expand freely in the air. The polyethylene foam product wasa cellular oval rod having a cross-section of 21 x 97mm. and was composed of substantially uniform fine individually-closed thin-walled cells. The foam had a density of about, 3 lbs./ cu. ft. 1
The product was tested for its self-extinguishing, properties by the following procedure: a sample of the product was inclined at a 30 angle below the horizontal while in a draft-free enclosure; a gas flame 1 in. high was applied to the lower end of the sample until it was ignited; the flame was then removed. The time for the ignited foam to extinguish itself was measured; this procedure was repeated a plurality of times on the foam. The selfextinguished times reported are an average of 30 tests.
The above product had a self-extinguishing time of 2 seconds.
For purposes of comparison, polyethylene foam was prepared and tested under similar conditions except for using 8 parts per 100 parts of polymer of antimony trioxide and 8 parts of chlorinated paraffin wax containing about 70 percent by weight of chlorine. The foam obtained by this procedure had a self-extinguishing time of 10.1 seconds.
' I claim: I
1. A foamed polyethylene article comprising (1) an an timony compound selected from the group consisting of antimony trioxide, antimony pentoxide and antimony sulfide, and (2) a halogen-containing aliphatic or cycloaliphatic compound having a hydrogen atom or halogen atom attached to a carbon atom o: to a halogen substituted carbon atom and containing from about 50 to 80 percent by weight of halogen, characterized in that it also contains (3) a bromine-containing aromatic or acyclic compound, the acyclic compound either containing vinyl bromine or not having a hydrogen or halogen atom attached to a carbon atom on to a bromine substituted carbon atom, the selfextinguishing agents being present in from 12 to 16 parts by weight per 100 parts of polyethylene and in ratios within the area ABCDEF of the accompanying drawing.
2. The article of claim 1, wherein the halogen of compound (2) is chlorine or bromine.
3. The article of claim 2, wherein the compound of (2) contains from 3 to 40 carbon atoms.
4. The article of claim 1, wherein the aromatic compound of (3) contains from 6 to 12 carbon atoms in the aromatic ring structure, and the acyclic compound of (3) contains from 3 to 15 carbon atoms.
5. The article of claim 1, wherein the compound of (2) contains from 3 to 40 carbon atoms and the halogen is chlorine or bromine, the aromatic compound of (3) contains from 6 to 12 carbon atoms in the aromatic ring structure, and the acyclic compound of (3) contains from 3 to 15 carbon atoms.
6. The article of claim 1 wherein the antimony compound is antimony trioxide.
7. The article of claim 1, wherein the compound of (2) is chlorinated paraflin wax containing about 70 percent chlorine.
8. The article of claim 1, wherein the compound of (3) is hexabromobenzene.
9. The article of claim 1, which contains 8 parts by weight of antimony trioxide, 6% parts by weight of chlorinated paraflin wax containing about percent chlorine, and 1% parts by weight of hexabromobenzene.
10. A foamed polyethylene article containing a mixture of self-extinguishing agents comprising (1) an antimony oxide selected from the group consisting of antimony trioxide, antimony pentoxide and antimony sulfide; (2) a member selected from the group consisting of a chlorinated parafiin wax containing between about 50 and percent by weight chlorine, hexachlorocyclohexane, pentabromomonochlorocyclohexane, hexabromocyclohexane, tris(2,3-dibromopropyl)phosphate and brominated polybutadiene latex, characterized in that the copolymer composition is a copolymer of from about 99 to 70 weight percent ethylene and from 1 to 30 weight percent of a vinyl alkanoate or alower alkyl acrylate or rnethacrylate, and 3) a bromine compound selected from the group consisting of hexabromobenzene, pentabromomonochlorobenzene, tetrabromodichlorobenzene, tetrabromobenzene, pen tabromophenol, tetrabromobisphenol-A, bis(pentabromopheny1)ether and tribromophenol, acyclic compounds having vinylic bromine or not having a hydrogen atom or bromine atom attached to a carbon atom cc to a bromine substituted carbon atom, pentaerythrityl tetrabromide, 2,2-bis (bromomethyl)-l-bromo-3-hydroxypropane, the self-extinguishing agents being present in from 12 to 16 parts by weight per 100 parts of polyethylene and in ratios within the area ABCDEF of the accompanying drawing.
References Cited UNITED STATES PATENTS 2,532,243 11/1950 Ott 260-25 2,590,211 3/1952 Rugar 252-8.1 X 2,669,521 2/ 1954 Bierly 106-15 2,894,918 7/1959 Killoran et al 260-25 2,962,464 11/ 1960 Feild 106-15 X 2,986,535 5/ 1961 Jacobson 260-25 3,137,745 6/1964 Johnstone 260-25 X 3,188,295 6/ 1965 Ballast 260-25 3,269,962 8/ 1966 Eichhorn 260-25 JOHN T. GOOLKASIAN, Primary Examiner D. J. FRITSCH, Assistant Examiner U.S. Cl. X.R.
161-403; 252-s.1; 260-285 D, 45.7 P, 45.75 R, DIG 24 P0405) UNETED STATES PATENT @FFEQE @EETEFEQATE @F QRT$N Patent No. 3,639,30h Dated 1 February 1972 InV I Charles F. Ralev. Jr.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line an, insert after "80".
Column 5, line Y, delete "extinguished" and insert -extinguishing-.
line 27, delete "vinyl" and insert --vinylic-.
Column 6, line 19, delete "alower" and insert a lower line 2?, insert -such asbetween "atom," and "pentaerythrityl" Signed and sealed this 22nd day of August 1972.
EDWARD M,FLEIGEER,JRQ ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents Patent No. 3,639,30h Dated 1 February 1972 Charles F. Ralev, Jr.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line ML, insert after "80" Column 5, line 7, delete "extinguished" and insert -extinguishing-.
line 27, delete "vinyl" and insert -vinylic-- Column 6, line 19, delete "slower" and insert a lower line 27, insert such as between "atom," and. "pentaerythrityl" Signed and sealed this 22nd day of August 1972.
EDWARD MELEIGEERJR. ROBERT GQTI'SCHALK Attesting Officer Commissioner of Patents
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3879345 *||Sep 6, 1973||Apr 22, 1975||Daicel Ltd||Self-extinguishing polystyrene resin composition|
|US3914513 *||Nov 20, 1973||Oct 21, 1975||Ici Ltd||Substrates coated with fire resistant compositions|
|US3925137 *||Mar 12, 1974||Dec 9, 1975||Agency Ind Science Techn||Method for producing flame-retardant fireproof clear coat|
|US3929689 *||Jul 5, 1974||Dec 30, 1975||Phillips Petroleum Co||Foamed flame retardant polyolefin compositions of improved physical strength|
|US4158077 *||May 17, 1977||Jun 12, 1979||White Chemical Corporation||Flame retardants for synthetic materials (I)|
|US4277569 *||Mar 10, 1980||Jul 7, 1981||Sentinel Foam Products Incorporated||Fire-retardant foam|
|US4324863 *||Sep 5, 1979||Apr 13, 1982||Societe Anonyme Dite: Les Cables De Lyon||Fire-proofed insulating material for an electric cable|
|US4348306 *||Apr 18, 1979||Sep 7, 1982||White Chemical Corporation||Flame retardants|
|US4446202 *||May 21, 1981||May 1, 1984||White Chemical Corporation||Process for rendering non-thermoplastic fibrous materials flame resistant to molten materials by application thereto of a flame resistant composition, and related articles and compositions|
|US4528300 *||Jan 31, 1984||Jul 9, 1985||The Dow Chemical Company||Process for producing dimensionally stable polyolefin foams using environmentally acceptable blowing agent systems|
|US4600606 *||Apr 10, 1984||Jul 15, 1986||White Chemical Corporation||Process for rendering non-thermoplastic fibrous materials flame resistant to molten materials by application thereto of a flame resistant composition, and related articles and compositions|
|US4871477 *||Oct 20, 1988||Oct 3, 1989||Firestop Chemical Corporation||Fire protected foamed polymeric materials|
|US5521003 *||Sep 4, 1992||May 28, 1996||Illinois Tool Works Inc.||Flame retardant composition|
|US5844009 *||Apr 26, 1996||Dec 1, 1998||Sentinel Products Corp.||Cross-linked low-density polymer foam|
|US5859076 *||Jun 11, 1997||Jan 12, 1999||Sentinel Products Corp.||Open cell foamed articles including silane-grafted polyolefin resins|
|US5882776 *||Jul 9, 1996||Mar 16, 1999||Sentinel Products Corp.||Laminated foam structures with enhanced properties|
|US5883145 *||Feb 25, 1997||Mar 16, 1999||Sentinel Products Corp.||Cross-linked foam structures of polyolefins and process for manufacturing|
|US5929129 *||Jul 12, 1996||Jul 27, 1999||Sentinel Products Corp.||Crosslinked foamable compositions of silane-grafted, essentially linear polyolefins blended with polypropylene|
|US5932659 *||Jun 21, 1996||Aug 3, 1999||Sentinel Products Corp.||Polymer blend|
|US5938878 *||Aug 16, 1996||Aug 17, 1999||Sentinel Products Corp.||Polymer structures with enhanced properties|
|US6004647 *||Jul 7, 1997||Dec 21, 1999||Sentinel Products Corp.||Polymer blend|
|US6054005 *||Apr 30, 1999||Apr 25, 2000||Sentinel Products Corp.||Polymer structures with enhanced properties|
|US6103775 *||Mar 16, 1999||Aug 15, 2000||Sentinel Products Corp.||Silane-grafted materials for solid and foam applications|
|US6167790||Oct 6, 1998||Jan 2, 2001||Sentinel Products Corp.||Laminated foam structures with enhanced properties|
|US6214894||Dec 21, 1999||Apr 10, 2001||Sentinel Products Corp.||Ethylene-styrene single-site polymer blend|
|US6316512||Apr 24, 2000||Nov 13, 2001||Sentinel Products Corp.||Silane-grafted materials for solid and foam applications|
|US6350512||Sep 5, 2000||Feb 26, 2002||Sentinel Products Corp.||Cross-linked polyolefin foam|
|US6359021||Apr 10, 2001||Mar 19, 2002||Sentinel Products Corp.||Polymer blend|
|US6472015||May 5, 1997||Oct 29, 2002||Sentinal Products Corp.||Cross-linked polyolefin tape|
|US6531520||Jan 25, 2002||Mar 11, 2003||Sentinel Products Corporation||Polymer blend|
|US7851558||Oct 23, 2006||Dec 14, 2010||Dow Global Technologies Inc.||Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer and polymeric foams formed from such blends|
|US20080287559 *||Oct 23, 2006||Nov 20, 2008||King Bruce A||Brominated Butadiene/Vinyl Aromatic Copolymers, Blends of Such Copolymers with a Vinyl Aromatic Polymer and Polymeric Foams Formed From Such Blends|
|DE4032315A1 *||Oct 11, 1990||Apr 16, 1992||Alveo Ag||Flammschutz-formulierung fuer organische polymere und ihre verwendung zur herstellung von brandfesten polyolefin-zusammensetzungen|
|EP0006558A1 *||Jun 18, 1979||Jan 9, 1980||BAYER ITALIA S.p.A.||Flame-resistant cross-linked olefin polymer foams and their manufacture|
|U.S. Classification||521/140, 521/88, 260/DIG.240, 521/89, 521/79, 521/907, 521/93, 521/149, 521/92, 521/98, 521/85, 521/143, 252/609|
|International Classification||E04B1/94, C08J9/00|
|Cooperative Classification||E04B1/94, Y10S521/907, C08J9/0095, C08J2323/06, Y10S260/24|
|European Classification||C08J9/00R, E04B1/94|